羰基化之外的羟甲基化：通过对映异位π-面识别实现铱催化甲醛与烯丙基乙酸酯的对映选择性还原偶联。
Hydroxymethylation beyond Carbonylation: Enantioselective Iridium-Catalyzed Reductive Coupling of Formaldehyde with Allylic Acetates via Enantiotopic π-Facial Discrimination.
作者信息
Garza Victoria J, Krische Michael J
机构信息
Department of Chemistry, University of Texas at Austin , Austin, Texas 78712, United States.
出版信息
J Am Chem Soc. 2016 Mar 23;138(11):3655-8. doi: 10.1021/jacs.6b01078. Epub 2016 Mar 9.
Abstract
Chiral iridium complexes modified by SEGPHOS catalyze the 2-propanol-mediated reductive coupling of branched allylic acetates 1a-1o with formaldehyde to form primary homoallylic alcohols 2a-2o with excellent control of regio- and enantioselectivity. These processes, which rely on enantiotopic π-facial discrimination of σ-allyliridium intermediates, represent the first examples of enantioselective formaldehyde C-C coupling beyond aldol addition.
摘要
由SEGPHOS修饰的手性铱配合物催化2-丙醇介导的支链烯丙基乙酸酯1a-1o与甲醛的还原偶联反应，以优异的区域和对映选择性控制生成伯高烯丙醇2a-2o。这些反应依赖于σ-烯丙基铱中间体的对映异位π-面识别，是除羟醛加成反应之外的首例对映选择性甲醛C-C偶联反应。
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